1. Field of the Invention
The invention relates to a method of improving the performance of agricultural compositions particularly with respect to rainfastness, run-off properties and efficacy under conditions of low humidity, by using silicone surfactants that reduce the surface tension to less than about 30 mN/m in 0.10% (w/w) aqueous solution thereof without concomitant spreading of the spray solution.
2. Description of the Related Art
Foliar-applied pesticidal and plant growth modifying chemicals are widely used in agricultural, industrial, recreational and residential areas worldwide. These chemical agents illustratively include insecticides, fungicides, herbicides, plant growth regulators and plant nutrients among other chemicals. Such chemicals are typically applied by spraying on the foliage of vegetation to be protected, controlled, killed or modified, but other methods such as rope-wick application are known. Some of these agents show contact action, killing, controlling or modifying the growth of target organisms at the site of deposition. Other chemicals are systemic, translocating within the plant to a site of action remote from the site of deposition. Still other chemicals show both contact and systemic action.
Surfactant formulations are commonly used in forestry, agriculture, and horticulture as agricultural adjuvants to improve the efficacy of agrochemical active ingredients such as micronutrients, growth regulators, biologicals, pesticides such as herbicides, fungicides, insecticides, acaracides and miticides. Surfactants are often used as dispersants, wetting and spreading agents, and emulsifiers in a formulated product or package or in a tank mix. Prior art identifies spreading of spray solution on the weed leaf as an essential criterion for surfactant efficacy. Surfactants have been used to improve herbicide performance since organic herbicides were first developed in the 1940s. Spreading the spray solution on weed leaves has always been a major reason for the inclusion of surfactants. This is clearly expressed in the preface to xe2x80x9cAdjuvants for Herbicidesxe2x80x9d Weed Science Society of America Monograph Series Number 1, 1988, R. H. Hodgson (ed). It includes the statement xe2x80x9cExperience shows that successful weed control often depends on the appropriate use of adjuvants in herbicide sprays to ensure uniform application and target coveragexe2x80x9d.
Herbicides commonly have been formulated with surfactants. Organosilicone surfactants provide surface tension values significantly lower than other commonly used surfactants. For example, the use of an organosilicone surfactant such as BREAK-THRU(copyright) S240, Goldschmidt Chemical Corp., or Silwet(copyright) L-77, Crompton Corp., in combination with a pesticide results in increased foliar uptake of the pesticide and, hence, increased efficacy of the pesticide in control of weed growth.
Among the numerous studies of the foliar uptake of the herbicide glyphosate combined with such silicone surfactants are those reported by Field and Bishop in Pesticide Science, 1988, Vol. 24, pp. 55-62; Stevens et al. in Pesticide Science, 1991, Vol. 33, pp. 371-82; Gaskin and Stevens in Pesticide Science. 1993, Vol. 38, pp. 185-92; and Gaskin and Stevens in Pesticide Science, 1993. Vol. 38, pp. 193-200. An extensive review of 160 references relating to the use of organosilicones as adjuvants for agrochemicals was provided by Stevens in Pesticide Science, 1993, Vol. 38, pp. 103-22. It is well recognized in the art that trisiloxane ethoxylate surfactants with no more than about 10 ethylene oxide units have the ability to impart the property of superspreading to agricultural spray mixtures. The term xe2x80x9csuperspreadingxe2x80x9d means the ability of a drop of the mixture to spread to a diameter at least 9 times as great as a drop of distilled water on a hydrophobic surface such as the leaf of a plant.
The fact that superspreading has been considered an essential attribute of such silicone surfactants is confirmed by the fact that various patents have been issued with improved spreading as the main objective. For example, U.S. Pat. No. 5,104,647 to Policello and U.S. Pat. No. 5,558,806 to Policello and Murphy have as main objective maintaining the superspreading capability of organosilicone/organic surfactant blends.
U.S. Pat. No. 5,017,216 to Dow Corning discloses postemergent herbicide compositions containing silicone glycol adjuvants, comprising blends of trisiloxane surfactants of the structure Me3SiOxe2x80x94SiMeRxe2x80x2xe2x80x94Oxe2x80x94SiMe3 wherein Rxe2x80x2 is a short-chain polyether radical with typically 4.6 ethylene oxide units, in combination with siloxane dispersants.
WO 89/12394, WO 99/40785, U.S. Pat. No. 6,051,533, U.S. Pat. No. 6,040,272 and EP 0483095, all to Monsanto, disclose various herbicide compositions comprising silicone surfactants in combination with other adjuvants like humectants, oils, glycol esters and organic cosurfactants. For the silicone surfactants claimed to be useful in these inventions, the inventors disclose a very broad structural range and provide little direction to those skilled in the art about which of these siloxane surfactants are to be advantageously used to enhance the efficacy of herbicide compositions. However, the examples used in these inventions are trisiloxanes like Silwet(copyright) L77 or Silwet(copyright) 408, having typical structures like Me3SiOxe2x80x94SiMeRxe2x80x2xe2x80x94Oxe2x80x94SiMe3 wherein Rxe2x80x2 a radical xe2x80x94(CH2)3xe2x80x94(CH2CH2Oxe2x80x94)8xe2x80x94Z wherein Z is hydrogen or methyl. It is well known to a person skilled in the art that trisiloxane surfactants of that type convey superspreading properties to aqueous solutions thereof, as long as the polyether chain length does not exceed about 10 ethylene oxide units. The fact that only such superspreading siloxanes have been chosen to exemplify the invention shows that the inventors were following the common belief that enhanced spreading is an essential attribute for silicone surfactants to be useful as adjuvants in herbicide compositions for most applications.
It is equally well-known to the practitioner of the art that silicone surfactants can have antagonistic effects on the efficacy on herbicides on certain plant species. Gaskin, et al., (Pestic. Sci. 1993, 38, 185-192) demonstrated that some trisiloxane ethoxylates (TSE), such as Silwet(copyright) L-77 surfactant (available from Crompton), can antagonize cuticular penetration of a herbicide into grasses, when compared to the herbicide alone. The term antagonism is used to indicate that the treatment of herbicide plus adjuvant is less effective than the comparative herbicide treatment. This tendency to antagonize the activity of glyphosate on some species in the absence of rain can be mitigated by the addition of a humectant such as glycerin to the spray solution, as disclosed in WO 89/12394. This addition prevents rapid drying of the spray solution which commonly is experienced when using superspreading silicone surfactants under conditions of low humidity, such as, for example, a relative humidity of 30% or less.
Gaskin, et al., (Pest. Sci. 1993, 38, 192-200) also studied the antagonism of glyphosate by trisiloxane surfactants with 8 to 40 ethylene oxide units and found that the antagonism is reduced when using surfactants with increased ethylene oxide content. However, no information was provided on rainfastness, and run-off behaviour of the glyphosate compositions, or on efficacy under conditions of low humidity.
It is also common knowledge that surfactants with high content of ethylene oxide groups usually have melting points above common use temperatures and thus are impractical to handle during application. Therefore it is usually desirable to use adjuvants which are liquid at room temperature.
Great Britain Pat. No. 1,255,249 to Dow Corning Corporation, published Dec. 1, 1971, discloses herbicide compositions employing silicone glycol copolymers. Here, general utility of a large number of adjuvants is professed, as exemplified by two generic silicone glycol formulas which embrace structures having both diorganosiloxane units and alkyl-glycol siloxane units. There are also provided two examples employing a triazine herbicide in conjunction with an adjuvant having 1.8 siloxy units and bearing a glycol chain consisting exclusively of 12 ethylene oxide units showing enhanced efficacy of the herbicide. However, no information is disclosed on rainfastness, and run-off behaviour of the herbicide composition, or on efficacy under conditions of low humidity. In addition, it is well known to the practioner of the art that such surfactants with a large number of only ethylene oxide units are solid at low use temperatures, such as 45 to 50 F., and thus impractical to handle.
It has now surprisingly been found that the use of silicone surfactants which reduce the surface tension in 0.1% (w/w) aqueous solution to less than about 30 mN/m without increasing the spreading properties results in a significantly improved performance of agrochemical compositions, such as herbicide compositions. The use of said siloxanes can improve, for example, the rainfastness, run-off, efficacy under conditions of low humidity without the need for additional humectants, and they can even be used in combination with cosurfactants which have an adverse effect on the spreading properties of superspreading silicone surfactants, and therefore offer a wider latitude of formulations.
It has further been found that silicone surfactants which are liquid at use temperature and reduce the surface tension in 0.10% (w/w) aqueous solution to less than about 30 mN/m without increasing the spreading properties thereof can especially advantageously be used to enhance the performance of agrochemical compositions, such as herbicide compositions. The use of said siloxanes can improve the efficacy, rainfastness, run-off, performance under conditions of low humidity without the need for additional humectants, and they can also be used in combination with cosurfactants which have an adverse effect on the spreading properties of superspreading silicone surfactants.
It is an object of this invention to provide a method for enhancing the performance of agrochemical compositions with respect to rainfastness, run-off, efficacy under conditions of low humidity without the need for additional humectants, by using silicone surfactants capable of reducing the surface tension of 0.10% (w/w) aqueous solutions thereof to less than about 30 mN/m without enhancing the spreading properties. It is a further object to provide a method for enhancing the performance of agrochemical compositions with respect to efficacy, rainfastness, run-off, efficacy under conditions of low humidity without the need for additional humectants, by using silicone surfactants which are liquid at use temperature and capable of reducing the surface tension of 0.10% aqueous solutions thereof to less than about 30 mN/m without enhancing the spreading properties.
Silicone surfactants which can be used within the scope of this invention, are polysiloxane-based surfactants containing polyether groups having such structural features that they are capable of reducing the static surface tension of a 0.10% (w/w) aqueous solution of the silicone surfactant to less than about 30 mN/m without enhancing the spreading properties thereof. In this invention, a silicone surfactant surfactant is defined as xe2x80x9cnot enhancing the spreading properties of a 0.10% aqueous solution thereofxe2x80x9d or as a xe2x80x98non-spreading silicone surfactantxe2x80x99 if the spreading area of a 0.10% (w/w) aqueous solution of said silicone surfactant on a polypropylene test substrate is reduced by a factor of about 10 or more, compared to a conventional super-spreading silicone surfactant such as Silwet(copyright) L-77 or Breakthru(copyright) S240, which is well known to the practitioner of the art as a typical super-spreading surfactant.
Preferred silicone surfactants capable of reducing the static surface tension of a 0.10% (w/w) aqueous solution of the silicone surfactant to less than about 30 mN/m without enhancing the spreading properties have the general structure:
xe2x80x83R3Sixe2x80x94Oxe2x80x94[RRxe2x80x2Sixe2x80x94Oxe2x80x94]nxe2x80x94Oxe2x80x94SiR3xe2x80x83xe2x80x83(I),
wherein
n is 1 to 3,
R is an alkyl radical with 1 to 6 carbon atoms,
Rxe2x80x2 is a radical of the structure
xe2x80x94(CH2)mxe2x80x94Oxe2x80x94(C2H4O)y(C2H3Rxe2x80x3O)zxe2x80x94Z,
xe2x80x83wherein
m is 2 to 6,
Rxe2x80x3 is independantly methyl, ethyl or phenyl,
Z is hydrogen, an alkyl radical with 1 to 4 carbon atoms, or an acyl radical with 2 to 6 carbon atoms,
y is 6 to 30, and
z is 0 to 10,
with the proviso that the ratio y/z is 1 or greater, and that the total number of alkylene oxide groups n*(y+z) in the siloxane polymer (I) is at least 12.
Preferred alkyl radicals for R and Rxe2x80x3 are methyl, a preferred value for m is 3.
A preferred subclass (a) are silicone surfactants (I), wherein
n is 1, R and Rxe2x80x3 is methyl, m is 3, y is 13 to 30, z is 0 to 2, especially preferred 0, and Z is hydrogen, methyl or acetyl.
Another preferred subclass (b) are silicone surfactants (I), wherein
n is 2, R and Rxe2x80x3 is methyl, m is 3, y is 6 to 20, z is 0 to 2, especially preferred 0, and Z is hydrogen, methyl or acetyl.
Another preferred subclass (c) are silicone surfactants (I), wherein
n is 1, R and Rxe2x80x3 is methyl, m is 3, y is 8 to 30, z is 2 to 10, and Z is hydrogen, methyl or acetyl, and the ratio y/z is 2 to 10 (i.e., 2:1 to 10:1), especially preferred 2 to 6.
Another preferred subclass (d) are silicone surfactants (I), wherein
n is 2, R and Rxe2x80x3 is methyl, m is 3, y is 5 to 20, z is 1 to 6 and Z is hydrogen, methyl or acetyl and the ratio y/z is 2 to 10, especially preferred 2 to 6.
Further preferred are any mixtures of two or more of the preferred subclasses (a to d).
Surfactants of subclass (c) and (d) have the additional benefit that the presence of propylene oxide units tends to reduce the melting point of the silicone surfactants, compared to materials containing only ethylene oxide units, resulting in materials with the desirable property of being liquid even at low use temperature such as 45 to 50xc2x0 F. so they are easy to handle during application.
Illustrative examples of siloxanes showing the required physical properties are shown below. These structures are given as typical examples, without intending to limit the scope of the invention:
xe2x80x83Me3SiOxe2x80x94[MeRxe2x80x2SiO]1xe2x80x94OSiMe3 with Rxe2x80x2=xe2x80x94(CH2)3xe2x80x94Oxe2x80x94(CH2CH2Oxe2x80x94)13xe2x80x94H
Me3SiOxe2x80x94[MeRxe2x80x2SiO]1.2xe2x80x94OSiMe3 with Rxe2x80x2=xe2x80x94(CH2)3xe2x80x94Oxe2x80x94(CH2CH2O)12(CH2CH(CH3)Oxe2x80x94)3xe2x80x94H
Me3SiOxe2x80x94[MeRxe2x80x2SiO]1xe2x80x94OSiMe3 with Rxe2x80x2=xe2x80x94(CH2)3xe2x80x94Oxe2x80x94(CH2CH2O)15(CH2CH(CH3)Oxe2x80x94)2xe2x80x94Me
Me3SiOxe2x80x94[MeRxe2x80x2SiO]1.3xe2x80x94OSiMe3 with Rxe2x80x2=xe2x80x94(CH2)3xe2x80x94Oxe2x80x94(CH2CH2O)15(CH2CH(CH3)Oxe2x80x94)2xe2x80x94C(O)CH3
Me3SiOxe2x80x94[MeRxe2x80x2SiO]2xe2x80x94OSiMe3 with Rxe2x80x2=xe2x80x94(CH2)3xe2x80x94Oxe2x80x94(CH2CH2Oxe2x80x94)9xe2x80x94H
Me3SiOxe2x80x94[MeRxe2x80x2SiO]2.2xe2x80x94OSiMe3 with Rxe2x80x2=xe2x80x94(CH2)3xe2x80x94Oxe2x80x94(CH2CH2O)8(CH2CH(CH3)Oxe2x80x94)2xe2x80x94H
It is well known to the practioner of the art, that the polyalkyleneoxide polymers have a broad molecular weight distribution and that the indices stated above designate the average composition only. The distribution of the different alkylene oxide units can be random or in blocks.
The siloxane surfactants described above can be prepared by methods well known to the practioner of the art, such as, for example, by hydrosilylation reaction of a Sixe2x80x94H containing siloxane and an unsaturated polyoxyalkylene derivatives, such as an allyl derivative, in the presence of a platinum catalyst. The reaction conditions and catalysts employed have been described in detail, for example, by W. Noll in xe2x80x9cChemie und Technologie der Siliconexe2x80x9d, 2nd ed., Verlag Chemie, Weinheim (1968), by B. Marciniec in xe2x80x9cAppl. Homogeneous Catal. Organomet. Compd.1996, 1, 487)xe2x80x9d or by G. C. Davis et al. in U.S. Pat. No. 5,204,438. It is common knowledge in the art that the hydrosilylation products of SiH-containing siloxanes with unsaturated polyoxyalkylene derivatives may contain excess unsaturated polyoxyalkylene derivative, or an isomerization product thereof. It is equally well understood that the linear siloxane derivatives, and the mixtures thereof, may contain up to 10%, preferred less than 5%, of cyclic siloxanes.
The siloxane surfactants described above may further be modified by introduction of units of the type
xe2x80x94[RRxe2x80x3Sixe2x80x94Oxe2x80x94]
wherein R has the meaning as stated above, Rxe2x80x3 is a linear or branched alkyl radical with 6 to 30 carbon atoms which may be additionally substituted by nitrogen atoms. Preferred radicals Rxe2x80x3 are alkyl groups with 10 to 18 carbon atoms, aminopropyl and dimethylaminopropyl. Modified siloxane surfactants can be prepared by methods well-known to the practitioner of the art, for example by equilibration of siloxanes (I) with linear or cyclic siloxanes or mono- or di-alkoxysilanes containing the units xe2x80x94[RRxe2x80x3Sixe2x80x94Oxe2x80x94], in the presence of an equilibration catalyst such as, for example, a hydroxide, or alkoxide of sodium, potassium or tetraalkylammonium, or by equilibration of the precursor SiH-containing siloxanes with siloxanes or alkoxysilanes containing the units xe2x80x94[RRxe2x80x3Sixe2x80x94Oxe2x80x94] in the presence of an acid or base catalyst, followed by hydrosilylation with an unsaturated polyoxyalkylene compound.
The use of the non-spreading silicone surfactants described above provides a method for enhancing the efficacy and rainfastness of agrochemical compositions in general and for reducing run-off from the plant which is commonly experienced when using superspreading silicone surfactants. They may be used to enhance the efficacy of agrochemical compositions under adverse conditions such as low humidity without the need for further humectants. If the non-spreading silicone surfactants contain significant amounts of propylene oxide units in their polyoxyalkylene side chain, the user has the additional benefit of having adjuvants which are liquid at low use temperature and thus easy to handle, without the need for solvents or additional premixing/dissolving.
The non-spreading silicone surfactants of this invention can be advantageously used with a variety of agrochemical compositions, such as compositions comprising micronutrients, growth regulators, pesticides such as herbicides, fungicides, insecticides, acaracides and miticides. Especially advantageous is the use in compositions comprising herbicides. Suitable herbicides are, for example:
Growth regulators such as:
Phenoxy Acetic Acids, such as 2,4-D [(2,4-dichlorophenoxy)acetic acid];
Phenoxy Propionic Acids, such as Dichlorprop[(RS)-2-(2,4-dichlorophenoxy) propionic acid], Mecoprop [(RS)-2-(4-chloro-o-tolyloxy)-propionic acid];
Phenoxy Butyric Acids, such as 2,4-DB[4-(2,4-Dichlorophenoxy)butyric acid];
Benzoic Acids, such as Dicamba [3,6-dichloro-o-anisic];
Other growth regulators, such as Fluroxypyr [4-amino-3,5-dichloro-6-fluoro-2-pyridyloxy-acetic acid], Picloram [4-amino-2,3,5-trichlor-2-carboxylic acid], Triclopyr [3,5,6-trichloro-2-pyridyloxyacetic acid], Copyralid [3,6-dichloropyridine-2-carboxylic acid];
Pigment Inhibitors: such as Amitrole, [1H-1,2,4-triazol-3-ylamine; 3-amino-1H-1,2,4triazole], Clomazone [2-(2-chlorobenzyl)-4,4-dimethyl-1,2-oxazolidin-3-one;2-(2-chlorobenzyl)-4,4-imethylisoxazolidin-3-one], Fluridone [1-methyl-3-phenyl-5-(a,a,a-trifluoro-m-tolyl)4-pyridone], Norflurazone [4-chloro-5-methylamino-2-(a,a,a-trifluoro-m-tolyl)pyridazin-3(2H)-one];
Mitotic disruptors, for example: Dinitroanilines, such as Isopropalin [4-isopropyl-2,6-dinitro-N,N-dipropylaniline], Oryzalin [3,5-dinitro-N4N4-dipropylsulfanilamide], Pendimethalin [N-(1-ethylpropyl)-2,6-dinitro-3,4-xylidine], Prodiamine [5-dipropylamino-a,a,a-trifluoro-4,6-dinitro-toluidine; 2,6-dinitro-N1N1-dipropyl-4-trifluoromethyl-m-phenylenediamine], Trifluralin [a,a,a-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine];
Inhibitors of lipid biosynthesis, such as Clethodim [(xc2x1)-2-[(E)-3-chloroallyloxyimino]propyl]-5[2(ethylthio)-propyl]-3-hydroxycyclohex-3-enone], Diclofop-methyl [(RS)-2-[4-(2,4-dichlorophenoxy)phenoxy]propionic acid], Fenoxaprop-ethyl [(xc2x1)-2-[4-(6-chloro-1,3-benzoxazol-2-yloxy)phenoxy]propionic acid; (xc2x1)-2-[4-(5-chlorobenzoxazol-2-yloxy)phenoxy]propionic acid], Fluazifop-P-butyl [(R)-2-[4-(5-trifluoromethyl-2-pyridyloxy)phenoxy)propionic acid, Haloxyfop-methyl [(RS)-2-(4-(3-chloro-5-trifluoromethyl 2-pyridyloxy)phenoxy]propionic acid], Quizalofop[.(RS)-2[4-(6-chloroquinoxalin-2-yloxy)phenoxy]propionic acid], Sethoxydim[.(xc2x1)-(EZ)-2-(1-ethoxyininobutyl)-5-[2(ethylthio)propyl]-3-hydroxycyclohex-2-enone];
Photosynthesis Inhibitors:
Triazines and s-Triazines such as Hexazinone [3-cyclo-hexyl-6-dimethylamino-1-methyl-1,3,4-triazine-2,4(1H,3H)-dione], Metribuzin [4-amino-6-tert-butyl-3-methylthio-1,2,3-triazine-5(4H)-one], Atrazine [6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine], Simazine [6-chloro-N2,N4-diethyl-1,3,5-triazine-2,4-diamine], Cyanazine 2-[4-chloro-6-ethylamino-1,3,5-triazin-2-yl]amino]-2-methylpropanenitrile, Prometon [N2,N24-di-isopropyl-6-methoxy-1,3,5-triazine-2,4,diamine], Ametryn [N2-ethyl-N4-isopropyl-6-methylthio-1,3,5-triazine-2,4-diamine];
Substituted ureas, such as Diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea], Fluometuron [1,1-dimethyl-3-(a,a,a-trifluoro-m-tolyl) urea], Linuron [3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea], Tebuthiuron [1-(5-tert-butyl, 1,3,4-thiadiazol-2-yl)-1,3-dimethylurea], Uracils, such as Bromacil [5-bromo-3-sec-butyl-6-methyluracil], Terbacil [3-tert-butyl-5-chloro-6-methlyuracil];
Other photosynthesis inhibitors, such as Bentazon [3-isopropyl-1H-2,1,3-benzothiadiazin-4(3H)-one 2,2-dioxide], Desmedipham [ethyl 3xe2x80x2-phenylcarbamoyloxycarbanilate; ethyl 3-phenylcarbamoyloxyphenylcarbamate; 3-ethoxycarbonylaminophenyl phenylcarbamate], Methazole [2-(3,4-dichlorophenyl)-4-methyl-1,2,4-oxadiazolidine-3,5-dione], Phenmedipham [methyl 3-(3-methylcarbaniloyloxy) carbanilate, 3-methoxycarbonylaminophenyl 3xe2x80x2-methylcarbanilate], Propanil [3xe2x80x2,4xe2x80x2-dichloropropionanilide], Pyridate [6-chloro-3-phenylpyridazin-4-yl S-octyl thiocarbonate];
Inhibitors of amino acid synthesis, such as Glyphosate, Sulfosate and other salts of N-(phosphonomethyl)glycine;
Sulfonylureas, such as Bensulfuron [a-(4,6-dimethoxypy-rimidin-2-ylcarbamoylsulfamoyl)-o-toluic acid], Chlorimuron [2-(4-chloro-6-methoxypyrimidin-2-ylcarbamoylsulfamoyl)benzoic acid], Chlorsulfuron [1-(2-chlorophenylsulfonyl)-3-(4-methoxy-6-methyl-1,3,5-triazin-2-yl) urea], Metsulfuron [2-(4-methoxy-6-methyl-1,3,5-triazin-2-ylcarbamoylsulfamoyl)benzoic acid], Nicosulfuron [2-(4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl)-N,N-dimethylnicotinamide; 1-(4,6-dimethoxypyrimidin-yl)-3-(3-dimethylcarbamoyl-2-pyridylsulfonyl)urea], Primisulfuron [2-(4,6-bis(difluoromethoxy)pyrimidin-2-ylcarbamoylsulfamoyl)benzoic acid], Sulfometuron [2-(4,6-dimethylpyrimidin-2-ylcarbamoylsulfamoyl)benzoic acid; 2-[3-(4,6-dimethylpyrimidin-2yl)ureidosulfonyl)]benzoic acid], Thifensulfuron [3-(4-kethoxy-6-methyl-1,3,5-triazin-2ylcarbamoylsulfamoyl)thiophen-2-carboxylic acid], Triasulfuron [1-(2-(2-chloroethoxy)phenylsulfonyl)-3(4-methoxy-6-methyl-1,3,5-triazin-2yl)urea], Tribenuron [2-(4-methoxy-6-methyl-1,3,5-triazin-2-yl(methyl)carbamoylsulfamoyl)benzoic acid];
Imidazolinones, such as Imazamethabenz [a reaction product comprising(xc2x1)-6-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-m-toluic acid and (xc2x1)-2-(4-isopropyl-4methyl-5-oxo-2-imidazolin-2-yl)-p-toluic acid], Imazapyr [2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2yl)nicotinic acid], Imazaquin [(RS)-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)quinoline-3-carboxylic acid], Imazethapyr [(RS)-5-ethyl-2-(4-isopropyl-4-methyl-5-oxo2-imidazolin-2-yl)nicotinic acid];
Cell membrane disruptors: Bipyridylium compounds, such as Diquat [9,10-dihydro-8a-diazoniaphenanthrene; 6,7-dihydrodipyrido[1,2-a:2xe2x80x2,1xe2x80x2-c]pyrazine-5,8-dium; 1,1xe2x80x2-ethylene-2,2xe2x80x2-bipyridyldiylium], Paraquat [1,1xe2x80x2-dimethyl-4,4xe2x80x2-bipyridinium(I)],
Diphenylethers, such as Acifluorfen [5-(2-chloro-a,a,a-trifluro-p-tolyoxy)-2-nitrobenzoic acid], Fomesafen [5-(2-chloro-a,a,a-trifluro-p-tolyloxy)-N-mesyl-2-nitrobenzamide; 5-(2-chloro-a,a,a-trifluoro-p-tolyoxy)-N-methylsulfonyl-2-nitrobenzamide], commercially available as REFLEX(copyright), Lactofen [ethyl 0-(5-(2-chloro-a,a,a-trifluoro-p-tolyl-oxy)-2-nitrobenzoyl)-DL-lactate], Oxyfluorfen [2-chloro-a,a,a-trifluoro-p-tolyl 3-ethoxy-4-nitrophenyl ether];
Cell wall inhibitors like Dichlobenil [2,6-dichlorobenzonitrile], Isoxaben [N-[3-(1-ethyl-1-methylpropyl)-1,2-oxazol-5-yl]-2,6-dimethoxybenzamide; N[(3-(1-ethyl-1-methylpropyl)isoxazol-5-yl]-2,6-dimethoxybenzamide];
Other herbicides such as Glufosinate [4-(hydroxy(methyl)phosphinoyl]-DL-homoalaine; DL-homoalanin-4-yl-(methyl)phosphinic acid], Bromoxynil, [3,5-dibromo-4-hydroxybenzonitrile]; 3,5-dibromo-4-hydroxyphenyl cyanide, 2,6-dibromo-4-cyanophenyl octanoate].
Aryltriazoliones such as carfentrazone-ethyl.
Especially preferred herbicides are N-(phosphonomethyl)glycine and its salts.
It is understood by those skilled in the art that the use of co-surfactants and co-adjuvants is common practice in spray tank mixes, pesticide formulations and within adjuvant blends. Therefore the scope of this patent is understood to include the use of the present invention in combination with other adjuvants, including but not limited to, surfactants, stickers, humectants, solvents, oils, drift control agents, buffers, extenders, deposition and retention aids, defoamers and antifoams, compatibility agents, and herbicide activity enhancers such as ammonium sulfate and nitrogen-containing fertilizers. Blends of other surfactants with these novel siloxanes is especially beneficial when a variety of properties may be desired from the adjuvant. Co-surfactants can include nonionic, cationic, anionic, and zwitterionic surfactants. Examples of potential co-surfactants include, but are not limited to the following: alkanolamides, alkyl aryl alkoxylates and their derivatives, alkoxylated amines and their derivatives, quaternary ammonium surfactants, alkoxylated quaternary ammonium surfactants and their derivatives, amine oxides, betaines and their derivatives, copolymers containing ethylene oxide, propylene oxide, butylene oxide, styrene oxide or any combination thereof, linear alcohol alkoxylates and their derivatives, branched alcohol alkoxylates and their derivatives, alkoxylated amides, alkoxylated fatty acids, alkoxylated fatty esters and oils, glycerol esters, alkoxylated glycerol esters, imidazolines and their derivatives, propoxylated quaternary amines, lignin and its derivatives (such as lignosulfonate salts), mono- and di-glycerides, olefin sulfonates, phosphate esters, alkyl polyglycosides, other siloxane surfactants (such as alkoxylated siloxanes, alkyl siloxanes, siloxanes containing betaine and quaternary ammonium groups, amino siloxanes, and alkoxylated amino siloxanes), sorbitan esters, ethoxylated sorbitan esters, sulfonate surfactants, sulfosuccinates and their derivatives, salts of fatty acids, and sarcosinates. By definition, the term xe2x80x98fattyxe2x80x99 as used in this invention includes materials of animal and plant origin.
In addition to being useful with the surfactants having no adverse effects on the spreading properties of herbicide compositions containing superspreading silicone surfactants, which are disclosed in U.S. Pat. Nos. 5,558,806 and 5,104,647 and are herein included by reference, the non-spreading siloxanes of the present invention can also be advantageously blended with surfactants that are known to antagonize super-spreading siloxanes. Examples of these include, but are not limited to: ethoxylated alkyl amines (such as Varonic(copyright) surfactants produced by Goldschmidt Chemical Corporation), ethoxylated alkyl quaternary ammonium surfactants, propoxylated quaternary ammonium surfactants (such as the Variquat(copyright) surfactants produced by Goldschmidt Chemical Corporation), ethoxylated alkyl aryl alcohols and their derivatives, linear and branched alcohol ethoxylates. By definition, the term alkyl as used in this patent can refer to both saturated and unsaturated hydrocarbon chains.
The method of this invention can be used for liquid and solid agrochemical compositions. They can be used in spray tank mixes, pesticide formulations, adjuvant blends, and in applications where the silicone surfactant is administered in a sequential addition after the application of the herbicide, such as disclosed in U.S. Pat. Nos. 5,985,793 and 5,821,195 which are incorporated herein by reference. Typical use temperatures are about 45xc2x0 F. to 100xc2x0 F.
Typical agrochemical formulations comprising non-spreading siloxanes and effective amounts of active ingredients can comprise, for example, 1 to 50% of siloxane(s), preferably 2 to 20% siloxane by weight of the total formulation.
If containing additional co-surfactants, typical adjuvant formulations comprising non-spreading siloxanes can comprise, about 1 to about 99% by weight of siloxane(s) and 0 to about 99% of co-surfactant(s), preferred about 10 to about 70% by weight of siloxane(s) and 30 to 90% of co-surfactant(s), especially preferred about 25 to about 50% siloxane(s) and about 50 to about 75% co-surfactant(s).